CN112811900A - p-n-BaTiO3/NiO heterojunction piezoelectric ceramic, preparation method thereof and application thereof in self-powered high-efficiency hydrogen production - Google Patents

p-n-BaTiO3/NiO heterojunction piezoelectric ceramic, preparation method thereof and application thereof in self-powered high-efficiency hydrogen production Download PDF

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CN112811900A
CN112811900A CN202110118320.7A CN202110118320A CN112811900A CN 112811900 A CN112811900 A CN 112811900A CN 202110118320 A CN202110118320 A CN 202110118320A CN 112811900 A CN112811900 A CN 112811900A
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piezoelectric ceramic
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金向华
刘守清
李华
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Suzhou Jinhong Gas Co Ltd
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Abstract

The invention provides p-n-BaTiO3a/NiO heterojunction piezoelectric ceramic, a preparation method thereof and application in self-powered high-efficiency hydrogen production. The heterojunction piezoelectric ceramic comprises n-BaTiO3The piezoelectric ceramic comprises a piezoelectric ceramic matrix and a p-NiO material forming a heterojunction with the piezoelectric ceramic matrix, wherein the mass fraction of the p-NiO is 0.1-10 wt%. The BaTiO provided by the invention3the/NiO heterojunction piezoelectric ceramic constructs a built-in electric field, has low recombination rate of charges and is piezoelectric-catalyzedThe chemical activity is high, and the hydrogen can be produced by piezoelectric catalysis by using water wave energy, sound wave energy and wind energy in the nature as driving forces. The prepared hydrogen has high purity, does not contain carbon monoxide, hydrogen sulfide, phosphine, chloride ions and other gases which poison the fuel cell, has simple and easy preparation method, is green and environment-friendly, and does not discharge substances which are harmful to the environment.

Description

p-n-BaTiO3/NiO heterojunction piezoelectric ceramic, preparation method thereof and application thereof in self-powered high-efficiency hydrogen production
Technical Field
The invention relates to p-n-BaTiO3a/NiO heterojunction piezoelectric ceramic, in particular to p-n-BaTiO3/NiO heterojunction piezoelectric ceramic material, preparation method thereof and vehicle-mounted self-bodyApplication in energy supply high-efficiency hydrogen production, belonging to the field of clean energy materials.
Background
The piezoelectric catalysis is a method for converting mechanical energy into chemical energy, namely, positive and negative charges are generated on the surface of a piezoelectric material under the action of external mechanical force, and the charges can accelerate the redox reaction of substances adsorbed on the surface of the piezoelectric material. The piezoelectric material can absorb mechanical energy such as sound, water waves, vibration and the like to generate charge separation, so that two sides of the piezoelectric material are charged with different signs.
However, piezoelectrically generated charges are easily recombined, resulting in poor piezoelectric catalytic efficiency. Therefore, technical means for improving the efficiency of the piezoelectric catalyst are necessary.
Disclosure of Invention
The invention aims to provide p-n-BaTiO for improving piezoelectric charge separation efficiency3the/NiO heterojunction piezoelectric ceramic material, the preparation method thereof and the application of the material in vehicle-mounted self-powered high-efficiency preparation of high-purity hydrogen overcome the defect of low piezoelectric catalysis efficiency caused by easy recombination of charges generated by piezoelectricity in the prior hydrogen preparation technology.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the p-n-BaTiO3the/NiO heterojunction piezoelectric ceramic material comprises n-BaTiO3The piezoelectric ceramic comprises a piezoelectric ceramic matrix and a p-NiO material forming a heterojunction with the matrix;
wherein the mass fraction of the p-NiO material is 0.1-10 wt%;
the thickness of the p-NiO is 0.1-10 μm.
Optionally, the upper limit of the mass fraction of the p-NiO material is selected from 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%; the lower limit of the mass fraction of the p-NiO material is selected from 0.1 wt%, 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%.
Optionally, the upper thickness limit of the p-NiO material is selected from 0.5 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm; the lower limit of the thickness of the p-NiO material is selected from 0.1 μm, 0.5 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm and 9 μm.
Alternatively, the BaTiO3The size of the piezoelectric ceramic substrate is 20mm × 20mm × 1 mm.
Optionally, the p-NiO is dispersed in n-BaTiO3A piezoelectric ceramic surface.
Optionally, the p-NiO is dispersed in n-BaTiO3One of the surfaces of the piezoelectric ceramic.
The p-n-BaTiO3The preparation method of the/NiO piezoelectric ceramic material comprises the following steps:
(1) preparation of BaTiO3And (3) particle: reacting barium salt and titanium salt with alkali to generate BaTiO3Greenware particles;
(2) and (3) granulation: adding the BaTiO prepared in the step (1)3Adding a certain amount of polyvinyl alcohol solution into the adobe particles, and then carrying out ball milling and granulation;
(3) preparing a greenware: BaTiO prepared in the step (2)3Adding the greenware particles into a mold with a certain size, and pressing the greenware particles into greenware by a film pressing machine under the pressure of 10-30 MPa;
(4) degumming: heating the ceramic blank to 450-DEG C and 500 ℃, and carrying out degumming treatment at constant temperature for 1-2 h;
(5) molding: after degumming, processing for 0.5h-2h at the temperature of 1150-1350 ℃, cooling and obtaining BaTiO3A ceramic;
(6)p-n-BaTiO3preparation of/NiO piezoelectric ceramics: in BaTiO3Uniformly coating a nickel salt solution on one side of the piezoelectric ceramic, drying, uniformly coating a NaOH solution on one side of the piezoelectric ceramic, and coating BaTiO3Surface formation of Ni (OH)2The film is sintered for 2 hours at 600 ℃ to obtain compact and uniform p-n-BaTiO3a/NiO ceramic.
(7) And (3) polarization treatment: adding p-n-BaTiO3Polarizing the/NiO ceramic plate for 20-60min at the voltage of 3-5 KV/mm, and standing for 24h to obtain p-n-BaTiO3the/NiO heterojunction piezoelectric ceramic.
Optionally, the barium salt is selected from BaCl2、Ba(NO3)2At least one of (1).
Optionally, the titanium salt is selected from at least one of titanium chloride and titanium nitrate.
Alternatively, the base is selected from NH3·H2At least one of O, NaOH and KOH.
Optionally, the nickel salt is selected from NiCl2、NiSO4、Ni(NO3)2、Ni(Ac)2At least one of (1).
Alternatively, the BaTiO3The particles are prepared by reacting barium chloride, titanium chloride and NaOH solution.
Alternatively, the concentration of the NaOH solution is in the range of 0.1-1.0 mol/L.
Alternatively, the BaTiO3The particles are made of barium nitrate, titanium nitrate and NH3·H2And O reaction.
Alternatively, the NH3·H2The concentration range of O is 0.1-2.0 mol/L.
Optionally, the mass concentration of the polyvinyl alcohol (PVA) solution is 4.0-8.0 wt%.
Optionally, the polyvinyl alcohol (PVA) solution has a mass concentration of 5.0 wt%.
Optionally, the polyvinyl alcohol (PVA) solution has a mass concentration of 6.0 wt%.
Optionally, the polyvinyl alcohol (PVA) solution has a mass concentration of 7.0 wt%.
Optionally, the polarization voltage is 3.0KV/mm, and the polarization time is 60 min.
Optionally, the polarization voltage is 4.0KV/mm, and the polarization time is 50 min.
Optionally, the polarization voltage is 5.0KV/mm, and the polarization time is 40 min.
Optionally, the preparation of the NiO film further comprises the steps of air drying after uniformly coating a NaOH solution, washing the surface of the NiO film by using deionized water, and then carrying out constant temperature treatment at the temperature of 400-450 ℃ for 20-60min to prepare the BaTiO3A NiO film on the surface.
Alternatively, the p-n-BaTiO3The application of the/NiO heterojunction piezoelectric ceramic in vehicle-mounted self-powered hydrogen production.
Alternatively, p-n-BaTiO at a temperature of 1-95 deg.C3The hydrogen production reaction system formed by the/NiO heterojunction piezoelectric ceramic material and the ammonia borane aqueous solution applies mechanical vibration or ultrasonic vibration to realize the preparation of hydrogen.
Optionally, the ultrasonic vibration frequency is 10-60 KHz.
Optionally, the upper frequency limit of the ultrasonic wave is 20KHz, 30KHz, 40KHz, 50KHz, 60 KHz; the lower limit of the frequency of the ultrasonic wave is 10KHz, 20KHz, 30KHz, 40KHz and 50 KHz.
Alternatively, the p-n-BaTiO3the/NiO is formed by BaTiO3And NiO constructed p-n junction.
Alternatively, a self-powered piezo-catalytic hydrogen production method, comprising the steps of:
(1) putting ammonia borane aqueous solution into a catalytic hydrogen production reactor, and adding p-n-BaTiO into the ammonia borane aqueous solution3the/NiO heterojunction piezoelectric ceramic material forms a hydrogen production reaction system, and then the reactor is sealed;
(2) adjusting the temperature of the reactor to 1-95 ℃, then pumping the system to vacuum, and adjusting the temperature in the reactor to 20-30 ℃ after the reactor reaches a vacuum state;
(3) and applying ultrasonic waves to a hydrogen production reaction system in the reactor to enable the hydrogen production reaction system to react and produce hydrogen.
In the present invention, p-n-BaTiO3The function principle of the/NiO heterojunction piezoelectric ceramic material is that the original electrically neutral material generates non-coincidence of positive and negative charge centers under the action of external force by utilizing the asymmetry of the structure of the material, so that two ends or two surfaces of the material have different charges. The mechanical vibration or the ultrasonic vibration realizes the conversion of mechanical energy and electric energy.
The reaction mechanism of the piezoelectric catalytic hydrogen production provided by the invention is that NH is carried out in the presence of a proper catalyst3BH3Hydrogen may be released by solvolysis or thermal decomposition, as shown in formula (I) below:
NH3BH3(aq)+2H2O(l)＝NH4 +(aq)+BO2 -(aq)+3H2(g) formula (I)
In the present invention, p-n-BaTiO3the/NiO heterojunction piezoelectric ceramic material is a catalyst with piezoelectric effect. The catalyst generates a piezoelectric effect in ultrasonic oscillation, a self-built electric field is formed in the material, and NiO has the functions of reducing the recombination rate of positive and negative charges and improving the separation efficiency of the positive and negative charges, thereby further improving the hydrogen production efficiency.
The hydrogen prepared by the method is high-purity hydrogen, and does not contain carbon monoxide, hydrogen sulfide and other pollutants which poison fuel cell electrode materials.
In one embodiment, the p-n-BaTiO prepared by the invention3the/NiO heterojunction piezoceramic material hydrogen production system is applied to running automobiles, converts vibration energy in the running process of the automobiles into electric energy, and then produces hydrogen through piezoelectric catalytic reaction to serve as automobile fuel to realize self-powered hydrogen production.
In one embodiment, the p-n-BaTiO prepared by the invention3the/NiO heterojunction piezoceramic material hydrogen production system is applied to a production workshop with large noise, and converts sound waves generated in the workshop production into electric energy to realize self-powered hydrogen production.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides p-n-BaTiO3the/NiO heterojunction piezoelectric ceramic material does not use a noble metal catalyst, has higher catalytic activity, reduces the production cost and maintains high-efficiency catalytic activity.
(2) The invention provides p-n-BaTiO3the/NiO heterojunction piezoelectric ceramic material can efficiently prepare high-purity hydrogen by utilizing mechanical energy such as water wave energy, wind energy, sound wave energy and the like in the nature, and realizes the collection and utilization of natural energy.
(3) The invention provides p-n-BaTiO3The preparation method of the/NiO heterojunction piezoelectric ceramic material is simple and easy to implement, green and environment-friendly, and does not discharge harmful substances to the environment.
Detailed Description
In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to provide technical solutions of the present invention. The technical solution, its implementation and principles, etc. will be further explained as follows.
The technical solution of the present invention is further explained below with reference to several examples.
The medicines used in the examples of the application are all commercially available.
Example 1
The p-n-BaTiO3The preparation method of the/NiO heterojunction piezoelectric ceramic material comprises the following steps:
(1) preparation of BaTiO3Greenware particles: reacting barium chloride, titanium chloride and sodium hydroxide to generate BaTiO3Greenware particles;
(2) and (3) granulation: adding the BaTiO prepared in the step (1)3Adding a certain amount of polyvinyl alcohol solution into the granules, and then carrying out ball milling and granulation;
(3) preparing a greenware: BaTiO prepared in the step (2)3Adding the greenware particles into a mold with a certain size, and pressing the greenware particles into greenware by a film pressing machine under the pressure of 10 MPa;
(4) degumming: heating the greenware to 520 ℃, and carrying out degumming treatment at constant temperature for 2 hours;
(5) molding: after degumming, processing for 2h at 1100 ℃, cooling to obtain BaTiO3A ceramic;
(6)p-n-BaTiO3preparation of/NiO piezoelectric ceramics: in BaTiO3One side of the piezoelectric ceramic is evenly coated with NiSO4Drying the solution, uniformly coating NaOH solution, washing the surface of the solution by deionized water, and then carrying out constant temperature treatment at 400-450 ℃ for 20-60min in BaTiO3Generating NiO film on the surface, sintering for 2h at 620 ℃ to obtain compact and uniform p-n-BaTiO3a/NiO ceramic;
(7) and (3) polarization treatment: adding p-n-BaTiO3Polarizing the/NiO ceramic plate for 60min under the voltage of 3KV/mm, and standing for 24h to obtain p-n-BaTiO3the/NiO heterojunction piezoelectric ceramic.
The hydrogen production reaction is as follows:
the method comprises the following steps: providing 100mL of NH at a concentration of 0.05mol/L3BH3Adding the solution into a reactor, and adding the p-n-BaTiO into the solution3the/NiO heterojunction piezoelectric ceramic material is covered with a quartz glass plate and the reactor is sealed;
step two: connecting the hydrogen production system and the low-temperature constant-temperature tank in the first step, sealing, controlling the temperature of the low-temperature constant-temperature tank to be 1 ℃, then pumping the system to be vacuum, and controlling the temperature of the system to be 25 ℃ through the low-temperature constant-temperature tank after the system reaches a vacuum state;
step three: and (3) placing the reactor in a 28KHz ultrasonic cleaner, turning on the ultrasonic, adjusting the hydrogen production system to a system circulation state, performing an experiment, and detecting the hydrogen yield of each hour by a gas chromatograph every other hour.
Example 2
The p-n-BaTiO3The preparation method of the/NiO heterojunction piezoelectric ceramic material comprises the following steps:
(1) preparation of BaTiO3Greenware particles: reacting barium nitrate, titanium nitrate and ammonia water to generate BaTiO3Greenware particles;
(2) and (3) granulation: adding the BaTiO prepared in the step (1)3Adding a certain amount of polyvinyl alcohol solution into the adobe particles, and then carrying out ball milling and granulation;
(3) preparing a greenware: BaTiO prepared in the step (2)3Adding the granules into a mould with a certain size, and pressing the granules into a greenware by a film pressing machine under the pressure of 15 MPa;
(4) degumming: heating the greenware to 450 ℃, and carrying out degumming treatment at constant temperature for 2 hours;
(5) molding: treating for 1h at 1200 ℃ after degumming, and cooling to obtain BaTiO3A ceramic;
(6)p-n-BaTiO3preparation of/NiO piezoelectric ceramics: in BaTiO3One side of the piezoelectric ceramic is uniformly coated with Ni (Ac)2Drying the solution, uniformly coating NaOH solution, washing the surface of the solution by deionized water, and then carrying out constant temperature treatment at 400-450 ℃ for 20-60min in BaTiO3Generating NiO film on the surface, and sintering at 550 ℃ for 2h to obtain compact and uniform p-n-BaTiO3a/NiO ceramic;
(7) and (3) polarization treatment: adding p-n-BaTiO3Polarizing the/NiO ceramic plate for 50min at the voltage of 4KV/mm, and standing for 24h to obtain p-n-BaTiO3the/NiO heterojunction piezoelectric ceramic.
The hydrogen production reaction is as follows:
the method comprises the following steps: providing 100mL of NH at a concentration of 0.05mol/L3BH3Adding the solution into a reactor, and adding the p-n-BaTiO into the solution3the/NiO heterojunction piezoelectric ceramic material is covered with a quartz glass plate and the reactor is sealed;
step two: connecting the hydrogen production system and the low-temperature constant-temperature tank in the first step, sealing, controlling the temperature of the low-temperature constant-temperature tank to be 1 ℃, then pumping the system to be vacuum, and controlling the temperature of the system to be 25 ℃ through the low-temperature constant-temperature tank after the system reaches a vacuum state;
step three: and (3) placing the reactor in a 28KHz ultrasonic cleaner, turning on the ultrasonic, adjusting the hydrogen production system to a system circulation state, performing an experiment, and detecting the hydrogen yield of each hour by a gas chromatograph every other hour.
Example 3
The p-n-BaTiO3The preparation method of the/NiO heterojunction piezoelectric ceramic material comprises the following steps:
(1) preparation of BaTiO3Greenware particles: reacting barium chloride, titanium nitrate and potassium hydroxide to generate BaTiO3Greenware particles;
(2) and (3) granulation: adding the BaTiO prepared in the step (1)3Adding a certain amount of polyvinyl alcohol solution into the adobe particles, and then carrying out ball milling and granulation;
(3) preparing a greenware: BaTiO prepared in the step (2)3Adding the greenware particles into a mold with a certain size, and pressing the greenware particles into greenware by a film pressing machine under the pressure of 20 MPa;
(4) degumming: heating the greenware to 500 ℃, and carrying out degumming treatment at constant temperature for 2 hours;
(5) molding: treating for 1h at 1150 ℃ after degumming, and cooling to obtain BaTiO3A ceramic;
(6)p-n-BaTiO3preparation of/NiO piezoelectric ceramics: in BaTiO3One side of the piezoelectric ceramic is evenly coated with NiCl2Drying the solution, uniformly coating NaOH solution, washing the surface of the solution by deionized water, and then carrying out constant temperature treatment at 400-450 ℃ for 20-60min in BaTiO3Generating NiO film on the surface, and sintering at 550 ℃ for 2h to obtain compact and uniform p-n-BaTiO3a/NiO ceramic;
(7) and (3) polarization treatment: adding p-n-BaTiO3Polarizing the/NiO ceramic plate for 20min under the voltage of 3KV/mm, and standing for 24h to obtain p-n-BaTiO3the/NiO heterojunction piezoelectric ceramic.
The hydrogen production reaction is as follows:
the method comprises the following steps: providing 100mL of NH at a concentration of 0.05mol/L3BH3Adding the solution into a reactor, and adding the p-n-BaTiO into the solution3the/NiO heterojunction piezoelectric ceramic material is covered with a quartz glass plate and the reactor is sealed;
step two: connecting the hydrogen production system and the low-temperature constant-temperature tank in the first step, sealing, controlling the temperature of the low-temperature constant-temperature tank to be 1 ℃, then pumping the system to be vacuum, and controlling the temperature of the system to be 25 ℃ through the low-temperature constant-temperature tank after the system reaches a vacuum state;
step three: and (3) placing the reactor in a 28KHz ultrasonic cleaner, turning on the ultrasonic, adjusting the hydrogen production system to a system circulation state, performing an experiment, and detecting the hydrogen yield of each hour by a gas chromatograph every other hour.
Example 4
The p-n-BaTiO3The preparation method of the/NiO heterojunction piezoelectric ceramic material comprises the following steps:
(1) preparation of BaTiO3Greenware particles: reacting barium chloride, titanium nitrate and ammonia water to generate BaTiO3Greenware particles;
(2) and (3) granulation: adding the BaTiO prepared in the step (1)3Adding a certain amount of polyvinyl alcohol solution into the adobe particles, and then carrying out ball milling and granulation;
(3) preparing a greenware: BaTiO prepared in the step (2)3Adding the greenware particles into a mold with a certain size, and pressing the greenware particles into greenware by using a film pressing machine under the pressure of 30 MPa;
(4) degumming: heating the greenware to 480 ℃, and carrying out degumming treatment at constant temperature for 2 hours;
(5) molding: treating for 1h at 1150 ℃ after degumming, and cooling to obtain BaTiO3A ceramic;
(6)p-n-BaTiO3preparation of/NiO piezoelectric ceramics: in BaTiO3One side of the piezoelectric ceramic is uniformly coated with Ni (NO)3)2Drying the solution, uniformly coating NaOH solution, washing the surface of the solution by deionized water, and then carrying out constant temperature treatment at 400-450 ℃ for 20-60min in BaTiO3Generating NiO film on the surface, and sintering for 2h at 600 ℃ to obtain compact and uniform p-n-BaTiO3a/NiO ceramic;
(7) and (3) polarization treatment: adding p-n-BaTiO3Polarizing the/NiO ceramic plate for 40min at the voltage of 5KV/mm, and standing for 24h to obtain p-n-BaTiO3the/NiO heterojunction piezoelectric ceramic.
The hydrogen production reaction is as follows:
the method comprises the following steps: providing 100mL of NH at a concentration of 0.05mol/L3BH3Adding the solution into a reactor, and adding the p-n-BaTiO into the solution3the/NiO heterojunction piezoelectric ceramic material is covered with a quartz glass plate and the reactor is sealed;
step two: connecting the hydrogen production system and the low-temperature constant-temperature tank in the first step, sealing, controlling the temperature of the low-temperature constant-temperature tank to be 1 ℃, then pumping the system to be vacuum, and controlling the temperature of the system to be 25 ℃ through the low-temperature constant-temperature tank after the system reaches a vacuum state;
step three: and (3) placing the reactor in a 28KHz ultrasonic cleaner, turning on the ultrasonic, adjusting the hydrogen production system to a system circulation state, performing an experiment, and detecting the hydrogen yield of each hour by a gas chromatograph every other hour.
Example 5
The p-n-BaTiO prepared in example 1 to example 43And (3) drying the hydrogen prepared from the/NiO heterojunction piezoelectric ceramic material, and then carrying out analysis and detection in a gas chromatograph, wherein impurity gases such as carbon monoxide, hydrogen sulfide, phosphine, chloride ions and the like are not detected.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, and are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims (10)

1. P-n-BaTiO3the/NiO heterostructure piezoelectric ceramic material is characterized by comprising n-BaTiO3The piezoelectric ceramic comprises a piezoelectric ceramic matrix and a p-NiO material forming a heterojunction with the matrix;
wherein the mass fraction of the p-NiO is 0.1-10 wt%;
the thickness of the p-NiO is 0.1-10 μm.
2. The p-n-BaTiO of claim 13The piezoelectric ceramic material with the/NiO heterostructure is characterized in that the p-NiO is dispersed in n-BaTiO3A piezoelectric ceramic surface;
preferably, the p-NiO is dispersed in n-BaTiO3One side of the piezoelectric ceramic.
3. A process for preparing the p-n-BaTiO of any one of claims 1-23The method for preparing the piezoelectric ceramic material with the/NiO heterostructure is characterized by comprising the following steps:
(1) preparation of BaTiO3Greenware particles: reacting barium salt and titanium salt with alkali to generate BaTiO3Greenware particles;
(2) and (3) granulation: adding the BaTiO prepared in the step (1)3Adding a certain amount of polyvinyl alcohol solution into the adobe particles, and then carrying out ball milling and granulation;
(3) preparing a greenware: BaTiO prepared in the step (2)3Adding the greenware particles into a mold with a certain size, and pressing the greenware particles into greenware by a film pressing machine under the pressure of 10-30 MPa;
(4) degumming: heating the ceramic blank to 450-DEG C and 500 ℃, and carrying out degumming treatment at constant temperature for 1-2 h;
(5) molding: degumming at 1150 deg.CProcessing for 0.5h-2h at the temperature of-1350 ℃, and cooling to obtain BaTiO3A ceramic;
(6)p-n-BaTiO3preparation of/NiO piezoelectric ceramics: in BaTiO3Uniformly coating a nickel salt solution on one side of the piezoelectric ceramic, drying, uniformly coating a NaOH solution on one side of the piezoelectric ceramic, and coating BaTiO3Generating NiO film on the surface, and then sintering for 2h at 600 ℃ to obtain compact and uniform p-n-BaTiO3a/NiO ceramic;
(7) and (3) polarization treatment: adding p-n-BaTiO3Polarizing the/NiO ceramic plate for 20-60min at the voltage of 3-5 KV/mm, and standing for 24h to obtain p-n-BaTiO3the/NiO heterojunction piezoelectric ceramic.
4. The p-n-BaTiO of claim 33The preparation method of the/NiO heterostructure piezoelectric ceramic is characterized in that the barium salt is selected from BaCl2、Ba(NO3)2At least one of;
the titanium salt is selected from at least one of titanium chloride and titanium nitrate;
preferably, the base is selected from NH3·H2At least one of O, NaOH and KOH.
5. The p-n-BaTiO of claim 33The preparation method of the/NiO heterojunction piezoelectric ceramic is characterized in that the mass concentration of the polyvinyl alcohol (PVA) solution is 4.0-8.0 wt%.
6. The p-n-BaTiO of claim 33The preparation method of/NiO heterojunction piezoelectric ceramic is characterized in that the nickel salt is selected from NiCl2、NiSO4、Ni(NO3)2、Ni(Ac)2At least one of (1).
7. The p-n-BaTiO of claim 33The preparation method of the/NiO heterojunction piezoelectric ceramic is characterized in that the preparation of the NiO film further comprises the steps of air drying after uniformly coating NaOH solution, washing the surface of the NiO film by deionized water, and then carrying out constant temperature treatment at the temperature of 400-450 ℃ for 20-60min to prepare the BaTiO3A NiO film on the surface.
8. The composition of p-n-BaTiO described in any one of claims 1 to 23A/NiO heterojunction piezoceramic material or p-n-BaTiO prepared according to any one of claims 3 to 73The application of the/NiO heterojunction piezoelectric ceramic material in self-powered hydrogen production.
9. Use according to claim 8, wherein the ultrasonic waves have a frequency of 10-60 KHz.
10. Use according to claim 8, characterised in that p-n-BaTiO3The application of the/NiO heterojunction piezoelectric ceramic material in vehicle-mounted self-powered hydrogen production.
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